The rocks that contain oil and gas in oil and gas reservoirs are porous and to remove the oil or gas from the reservoirs requires that the oil or gas move through the pores in the rock. If the pores are blocked, then it is difficult and it may even become impossible to remove the oil or gas from the reservoir, with consequent economic loss to the oil or gas well owner.
Two notorious contaminants that may block the pores are waxes and asphaltenes. A wax is normally defined as a hydrocarbon that is a solid at room temperature and has 20 carbon atoms or more. An asphaltene is an agglomerate of aromatic hydrocarbons, and may contain bound oxygen, nitrogen and sulphur atoms. The oil and gas in many, if not most, reservoirs contains both waxes and asphaltenes. These waxes and asphaltenes may be dissolved in the oil. In some cases, however, the waxes and asphaltenes may partially block the pores, or, as production continues, the very action of removing oil from a reservoir may cause waxes and asphaltenes to precipitate out of solution and block the pores.
Also, the waxes and asphaltenes may precipitate out of solution in the well bore itself, or in equipment used for the production of oil and gas and reduce or block the flow of oil from the well.
The economic damage from waxes and asphaltene precipitation can be very high, killing some wells entirely. Consequently, a great deal of attention has been devoted to developing cost effective ways of preventing waxes and asphaltenes from precipitating out of solution or of removing the waxes and asphaltenes from an oil reservoir or well bore.
One such attempt at a solution has been to apply to a well a mixture of a significant proportion of the aromatic xylene (about 45%) and a lesser proportion of the paraffinic hydrocarbon hexane (about 30%), together with about 25% methanol. This product is known by the name NP760 and is available from Wellchem of Calgary, Alberta, Canada. The xylene is intended to solvate asphaltenes and the hexane is intended to solvate waxes. The xylene and hexane components of the composition are each derived from refining a feedstock and removing that particular component from the feedstock. The result is a product that has moderate success in solvating at least some waxes and asphaltenes, but because the fluid is made from a complex process, the fluid is relatively expensive.
One difficulty with the use of hexane or other alkanes is that they tend to cause asphaltenes to precipitate out of solution. This in turn is believed to increase the precipitation of waxes. How this is believed to occur is as follows. Waxes require nucleation sites in the oil formation or well bore to which they can attach. Any such site will become a nucleation site for the further accretion of waxes. In time, the waxes, mixed with asphaltenes, build outward and block the well bore or pores in the formation. In a typical oil formation water surrounds the rock in the formation and waxes will tend to slide off the water and not attach to the rock. However, if asphaltenes are present, they may attach to the rock surface since reservoir rock contains positively and negatively charged molecules (cations and anions) which attract the polar asphaltenes. The asphaltenes may then protrude beyond the water layer surrounding the rock particle and form a nucleation site for waxes. Hence a precondition for wax deposition is the precipitation of asphaltenes from the oil in the reservoir. It is the hexane that causes the precipitation of the asphaltenes and thus the formation of nucleation sites for waxes. The xylene is added to solvate the asphaltenes and prevent the formation of nucleation sites.
However, such a product, formed of an alkane (particularly pentane, hexane and heptane) and an aromatic, and similar products that are produced by the steps of: (a) refining a feedstock, (b) selectively removing hydrocarbons and (c) subsequently mixing the selected hydrocarbons, are not believed very effective in removing gummy layers of waxes and asphaltenes that are typically found in oil and gas reservoirs and well bores in relation to their cost. The waxy depositions in oil and gas formations are complex aggregations of molecules, with many layers and globules of different waxes and asphaltenes, which the inventors have found are not readily removed by simple compositions. Such products, requiring several processing steps, tend to be expensive. Also, in some wells such mixtures of an aromatic, alkane and alcohol or other polar substance may increase the precipitation of waxes and asphaltenes. Thus for example, in the general case, stabilized C.sub.5 + condensates tend to precipitate asphaltenes, with the future risk of wax contamination for the reasons just mentioned. That is to say, while it is possible to tailor a particular composition of alkanes and aromatics to a particular well formation, such a procedure is relatively expensive and may produce a product that is useful for one well formation but not for another. With the expense of the product and the risk of actually damaging the well, the application of such a product to a well is a venture not lightly undertaken.
The inventors have found a composition and a method for its use that helps to remove the uncertainty from applying wax solvating materials to wells, while at the same time significantly reducing the cost of making and using the composition. The composition is formed from a complex mixture of aromatics and alkanes (preferably C.sub.7 +). The complex mixture provides different components that solvate different waxes and asphaltenes. Rather than using a composition derived from selecting individual components during refining, the composition is the residue after lighter hydrocarbon components (preferably substantially all C.sub.1, C.sub.2, C.sub.3, C.sub.4 and C.sub.5 hydrocarbons) have been removed during refining. With the appropriate selection of the feedstock, an improved wax solvating and asphaltene solvating composition may be derived.
The feedstock should be selected to have a significant proportion of aromatics and alkanes. The inventors have found that if a feedstock has a mass percentage of trimethylbenzene higher than the mass percentage of n-decane as determined by gas chromatography then the feedstock will have a sufficiently complex mixture of aromatics and alkanes for the efficient solvating of asphaltenes and waxes, particularly after the lighter ends (C.sub.1, C.sub.2, C.sub.3, C.sub.4 and C.sub.5 hydrocarbons) have been removed by distillation from the feedstock. By a sufficiently complex mixture of aromatics is meant aromatics other than, but not necessarily excluding, the simple aromatics benzene, toluene, ethylbenzene and xylene. These simple aromatics are the aromatics normally measured in gas chromatography since they usually yield well defined peaks. The inventors have found that it is necessary to have a good quantity of other aromatics, and the presence of these other aromatics is indicated by the quantity of trimethylbenzene.
Another indication that a feedstock contains a suitably complex blend of aromatics and alkanes to solvate complex gummy layers of waxes and asphaltenes is the presence of sulphur containing compounds in the feedstock. It is believed that sulphur is a catalyst for the conversion of alkanes to aromatics during the many years that the hydrocarbon deposit evolves underground. Hence, the more sulphur, the greater the conversion of alkanes to aromatics. Thus the presence of sulphur is an indication that the feedstock will have a suitable proportion of aromatics to alkanes.
Aromatic composition and alkane composition should be in the range 30% to 70% by mass percentage as determined by gas chromatography for a suitable composition. However, it is not believed that such a range of aromatics and alkanes is sufficient: the composition must be suitably complex as noted above. Further, it has been found desirable that the feedstock be clear or have a light colour such as amber. Dark colour indicates the presence of heavy ends (C.sub.16 +) that assist in the formation of waxes. The C.sub.16 + content of the fluid should preferably be below 2% by mass as determined by gas chromatography. If the feedstock contains greater than 2% C.sub.16 + content, then an additional cut may be taken to remove all or substantially all the higher ends.
Alternatively, the fluid may be formulated for pure asphaltene solvation. Pure asphaltene generally occurs in only two situations in the reservoir. In one case, pyrobitumen can be present in gas reservoirs. This is generally believed to have been deposited long ago when oil which had occupied the reservoir migrated out and left the pyrobitumen behind. This pyrobitumen can move during production and plug the formation or wellbore.
Another case is in tertiary recovery using hydrocarbon miscible solvents floods. Light hydrocarbons in the C.sub.2 to C.sub.5 hydrocarbons range are injected into the reservoir to push the oil to production wells. While these light hydrocarbons will solvate paraffinic molecules they act to precipitate asphaltenic molecules. Thus asphaltene will precipitate without heavy paraffinic molecules present.
The fluid is formulated for solvating pure asphaltenes by increasing the temperature of the cutpoint. This removes the C.sub.6 and C.sub.7 components which contain a lower percentage of aromatics than the bulk residue. The aromatics in this region are small and not as effective as the more complex aromatics in the remainder of the fluid.
Asphaltenes are normally colloidally suspended in crude oil by peptizing resins (maltenes). These peptizing resins are aromatic and polar at one end and paraffinic or neutral at the other end. The polar end is attracted to the asphaltene and the nonpolar end to the crude oil. When the solid asphaltene is completely surrounded by peptizing resins it becomes a colloidally suspended particle completely suspended in the crude oil.
Currently the main way of treating these precipitations is by injecting pure xylene down a well. Xylene is a simple aromatic with short paraffinic side chains. The more complex aromatics in the C.sub.8 + fluid described here with longer side chains provide superior emulation of the maltenes that originally suspended the asphaltene molecules than just pure xylene.